Concentration of wood sugar solutions



July 12, 1960 T. RIE'HM 2,944,923

CONCENTRATION OF WOOD SUGAR SOLUTIONS Fi ed Ja 17, 1958 Y T rlzlf Q l United States Patent O v 2,944,93 i co1-IcE1\I'mA'r1o1-r or woon SUGAR SOLUTIONS Theodor Riehm, Mannheim, Germany, assigner to Udic Societe Anonyme, Vevey, Switzerland The invention `relates to the evaporation and concentration of acid wood sugar solutions.

i YIn the wood hydrolysis with vconcentrated hydrochloric acid according to the Bergius-Rheinau process, there `are obtained sugar solutions in hydrochloric acid, which vhas to be separated from the lsugars and recovered. Heretofore, said hydrochloric acid Was evaporated in. a single step vacuum distillation at a` pressure of about 40 to 50 Torr. and a temperature of about 40 to 50 C. This type of operation requires a relatively large heat supply and increases the cost of the. sugar production.

Methods are known to concentrate solutions in several vacuum or alternating pressure and vacuum steps, whereby the euents of the steps operated at higher pressures and temperatures are used to heat the solution in the steps operated at lower temperatures. In this way, the heat economy of the whole evaporation is improved beice second pressure release valve or throttle into a vacuum stage at 30 to 50 Torr., wherein it is evaporated to the iinal concentration in a conventional circulation evaporator.

The whole apparatus represents a multiple-effect evaporator where the vapors of the rst stage heat the second stage, and the vapors of the second stage heat the third stage; in this way, the entire heat steam requirement is only about one third that of a single-stage evaporation. y Y Y It has been found that any length of residence time of the sugar solution in the separatorV is still more harmful than such residence timein the evaporator tubes because even at low level ofthe liquid in the separator the safe residence time is exceeded. For this reason,- the throttles between `the pressure stages are opened usui# ciently to ensure that the entire solution passes imme diately into the next evaporator, even though this may allow a slight escape of the vapors from the higher to the lower pressure stage. A particular advantage of the novel evaporation systern is that no pumps are required to convey the liquid from stage to stage.

cause external heat has to be supplied only to the first evaporation step. This conventional type of multiple step operation is not suitable for the concentration of acid Wood sugar solutions because the sugars are decomposed at the required high temperatures of the first evaporation steps.

lIt is a principal object to provide a method of evaporating the Ibulk of the concentrated hydrochloric acid from wood sugar solutions in several stepsv under conditions -where no harmful decomposition of the sugar takes place.`

' Other objects and advantages will -be apparent from a consideration of the specification and claims.

According to the invention, the wood sugar solution is'passed in a single passage at atmospheric pressure up- `wardly through externally heated long narrow evaporavtor'tubes in which it partially evaporates. The generated acid vapor and the lliquid passthe'tubes within fractions 'of` a second at such speed thatY no liquid can `fall back V-into the tubes and that'substantially no decomposition of the sugars takes place. The evaporation uses'the-principle'of the so-called Mammoth pump yas the specific ac- ;tion is due to the dilerence of the specific weights lof 'the sugarsolution andthe '.rnixture of sugar "solution and hydrochloric Y acid vapor in; the individual tubes., The liquid passes'at a` rate 0f 2040"m. /vsec. through the ,evaporator tubes.` This acceleration of'the liquid particles in the evaporator tubes prevents the formation of Ysugar decomposition products and their precipitation on the walls of the tubes, which precipitation is responsible ',for the obnoxious cake'deposits in other evaporators.

From the evaporator, the liquid-vapor mixture passes tangentially into a separator, where the solution and ivapors are separated in known manner. The solution which contains still hydrochloric acid, is immediately which corresponds-to a residence time ofabout .5 to 3 passed. through a release valve or throttle'into a second i bevaporator, which is similar to the rst evaporator and "operated at about 100-250 Torr. Said second evapora- "torfis also passed ina single passage whereby further amounts'of acid are evaporated. After separation of the In the conventional one-stage vacuum concentration at 40 to 50 C., the HCl vapors developed from l0-441% hydrochloric acid cannot Ibe precipitated in vacuo without addition of water; they are recovered only as dilute 30% HCl, which has to be concentrated up to 4041% HC1 in a separate heat-consuming operation. It is an additional advantage of the method of the invention that in the iirst concentrationstep, in addition to relatively high concentrated condensed acid, gaseous HCl is obtained which can be directly used to obtain 41% HC1 Without requiring additional heat for evaporation.

Reference is made to the accompanying drawing showing by way of example suitable apparatusv to carry out the invention. 7

' In the drawings,

Fig. 1 shows diagrammatically a multiple stage multiple effect evaporator for the concentration of hydrochloricacid-wood sugar solutions;

Figs. 2 to 4 show cross-sections of various evaporator tubes.

In Fig. 1, the reference numeral 1 designates an evaporator operated under atmospheric pressure, which consists, for instance, of graphite tubes of about 3 to 6 m. length and about 8 to 20 mm. inner diameter. The tubes, which maybe built up yfrom several individual sections, are heated from the outside with steam of l40-1-50` C. The acid sugar solution enters the tubes from'the bottom and passestherethrough at. a rate of l0 to 40 n1./sec.,

sec. Solution and hydrochloric acid vapors Venter the separator 2, which has a temperature of about 100 "to 108 C. The thickened sugar solution Iows, without formation of a liquid level, at once over the throttle 3 into the bottom of evaporator 4, which has the same construction as on evaporator, but is operated at apressure of about 100-250 Torr. The solution passes upwardly through the evaporator 4 at the same rate as in evaporator 1 and is heated by the vapors coming from separator 2. Y Said vapors are at least'in part condensed in the evaporator and pass with a temperature of about 60 to 100 C. into the separator 7. It the sugar solution entering evaporator l-had a concentration ofmore than 30% HCl, there remain in'the separator V7 still uncondensed vapors which are drawn oi upwardly whereas an aqueous about 33% HClv solution is siphoned 01T.

Fromv theevaporator 4, the concentrated sugar solution and the HC1 vapors enter with a temperature of about .60 to C. Athe separator 5 from which the sugar solu- 4acidivaporsythe remaining solution 'is transferred overa i tion ows through the throttle valve 6 into the bottom of evaporator 8, which is heated by the overhead HC1 vapors of the separator 5 entering at 1l. Said evaporator 8 is a conventional circulating evaporator and operated at about 30-to 50 Torr. and a temperature of -fabout 35 to 50 C. The developed HC1 vvapors larevdrawn offat 9 andthe concentrated acid-free sugar solution leaves at 10. In said third evaporation stage, the concentrated sugar solution is so viscous as -to rprevent the .use of the long narrow tubes of the evaporators 1 and 4. Tubes of larger diameter have to vbe employed to which the principle of single passage operation cannot be applied.

To improve the heat economy of `the plant, itisfof ad-` vantage tok pass thev starting solution before entering into the evaporator l Ain heat `.exchange with the vapors or condensates leavingthe separators 7 and/or 8. u

Whengraphite tubes are used in .the evaporators `1, the inner diameter of the vertical tubes should not ex4 ceed l1 5 mm. and the steam temperature should be at least 140 C. to ensure a uniform rapid passage of the solution so as to prevent falling back of individual dropletsofl the liquid. With Wider tubes, the residence times of the liquid may become so long as to produce decomposition of the sugars at the employed high temperatures.

yIn order to reduce further the residence time of the solution inthe evaporator tubes, the inner space of the of 180 Torr., 2.4 kg./hour of vapors containing 29% of HCl'were distilled off, and the same amount of vapors, which contained of'iHCl, was distilled from the evaporator 8, which had a temperature of 40 C. and was operated under a pressure of 45 Torr.

5.4 kg. of sugar solution.containing 37% of sugars passed per hour from the evaporator 4 into the evaporator 8, and 3 .kg/hour of concentrated 661% sugar :solution were withdrawn from evaporator 8. Y p

'The temperature in the :separators '2 and"7 `was 107 C. and 65 C., respectively.

The residence iltimel .of ithe'solution in; evaporators 1 and4 eachwas 1-5 seconds. u y, u

The loss 'of sugarsin the etitire'operation'was .1%.

Example 2 Y A The same apparatus was used as in Example l, and the same temperature, ow .and pressure, conditions were maintained. p 12.5 lig/hour of a prehydrolysis pine .wood sugar solution were fed into vevaporator .1 at atmospheric pressure and heated with steam of .a temperature of '150 -.C. The

l solution hada sugar-concentration of 12% and ahydro- -tubes may be narrowed by providing therein rods 12, 13, v

14 of various forms, as illustrated in Figures .2 to 4, which rods should have as little contact as possible with the inner walls, for instance by provision of spacers 15.

The method of the invention has been developed for concentrating the sugar solutions obtained inthe pre*- hydrolysis and main hydrolysis of wood with medium concentrated and high` concentrated hydrochloric acid, respectively, as for instance described in my application Serial No. 705,515, for Process for the Sacchariiication of Softwood Sawdust, tiled December 27, 1957. In the concentration of the main sugar solutions, which contain essentially glucose and some other sugars, particularly xylose, in minor amounts, substantially Ano .decomposition is observed when the concentration is carried yout according to the invention. In the concentration ofthe particularly sensitive prehydrolysis sugar solutions ob -tained from hard-wood, which consist yessentially of xylose and to 35% HC1, vsome slight loss .of Xyl'ose cannot be avoided; such loss does not exceed vabout .75% per concentration stage. In contrast to sugar syrups :obtained from such prehydrolysis solutions 'in conventional 'circulating evaporators in a single. concentration 'stage .under reduced pressure at about 45 1C., the prehydrolysis sugar syrup obtainedaccordin'g to ythe invention represents a water-clear acid-free liquid which does `not require the conventional subsequent expensive purication Procedure.' f

The invention is illustrated by the following examples. It should be understood, however, rthatltheinvention is chloricacid concentration .of 28% .of IHCl. The sugars consisted of 27% of glucose', 35% of mannose, .5% .of galactose, 29% of xylose, and 4% of varabinose.

In said evaporator 1, 4.5 lig/hour of .hydrochloric acid containing 40% vof HC1 were evaporated. 8 kg./hour.of

sugarsolution Acontaining 18.7% of sugarsentered evaporator 4.

.In `evaporator 4, 2.8 lig/,hour of vapors containing 26.5% of HC1 were `distilled off, and 5.2 `kg./hour of sugar solution containing 28.7% of sugars were passed not to be considered as limited tothis particular type i of solutions'to `be concentrated.

j All parts are given by weight unless specified otherwise.

Example 1 -1 at atmospheric pressure and heated with steam -of a temperature of 150 C. The solution had a concentration-of 16.6% of sugars and 33.4% of iHCl. The sugars were composed of 90% of glucose, 7% of Xylose, 2% of farabinose and 1% of mannose. From the evaporator, 4.2 kg. of -HCl vapors containing 58% .of HC1 were drawn ofI per hour, and 7.8 kg. of sugar solution containing 26% of sugars passed hourly into the second evaporator 4, where it was heated by the Vvapors Vcoming from .the

`iirst evaporator and having a temperature 'of 107 C.

In the second evaporator 4, which was yof 'thesame construction as evaporator y1 andioperated at. afpressupe into the evaporator 8. `From said evaporator 8, V2.7 kg./hour of vapors containing 26% of .HC1 were drawn oil?, and 2.5 lig/hour of a 60% vsugarsolution was recovered. Y The lloss of sugars was .16%. Said loss during `concentration of the solutions can be .further reduced by Apassing the solutions not upwardly `but downwardly through the evaporators 1 and 4.

Y l. A process for concentrating a sugar solution-'obtained in the hydrochloric acid'saccharitication ,of cellulosic materials comprising passing said solutionsubstantially under atmospheric pressure upwardly at a rate of about `10 rvto 40 m./sec. through a first set .of narrow vertical tubes having a diameter of about 8-to 20 mm. and heated at a temperature of aboutI10O to 150 C., said rate of ow preventing backiiowotsaid solution ,intosaid tubessepa- Arating the `g'eneratedvapors.from the solution, transferring the thus separated solution vat ksubstantially the rate o f separation, so as to preventuaccumulationthereof in the separation zone,continuou,sly ,substant-iallyrwithout in- 'termediatestoppage into -a second vset of narrow vertical tubes, heating said secondsetfof tubes with said .generated vaporsLpassingsaid solutionat a pressure .of kabout 100 -to 250-Torr. upwardly through said second setof tubes, withdrawing vapors from the solution. leaving vsaidsecond setiof tubes, i feeding theremaning .solution finto .a-.cir- `culating yevaporator maintained 4at .a ,pressure of about .3010-50 [`orr.,` heating said .circulating .evaporator Ywith rsaid withdrawing vapors, and Vdrawing oli concentrated sugar-syrup and Yhydrochloric acid vapors fromsaid circulating evaporator.

2. A .processes .defined in claim ,1 wherein Ysaid narrow verticaltubesconsist ofgraphite and have a length foi3to6m...k Y g. i3. A process as defined in claim l comprising 'providing in said vertical .tubes ,inner rods reducing the Jfree rcross section of said tubes.

4. LA process for .concentrating a sugar solution `ob- .tainedin the :hydrochloric acid saccharication .of .cel- `lulosic materials comprisngpassingsaid solutioninsepafrate tconiined ystreams .having a `diameter Snot substantially exceeding ...-115 nipwardly Waugh f-.a first V4\evaporation Zone maintained substantially at atmospheric pressure and at a temperature of about 100 to 150 C. at a rate producing a residence time of about .5 -to 3 seconds and preventing backiiowof said solution, combining said streams at the head of said irst evaporation zone, drawing oli the vapors developed in said first evaporation Zone, passing the remaining solution in continuous substantially undammed flow into a second evaporation zone maintained at a pressure of about 100 to 250 Torr., heating said second evaporation zone with the vapors of said first evaporation zone at a temperature of about 60 to 80 C., passing the solution in separate coniined streams of substantially the same diameter and at substantially the same rate as in said tirst evaporation zone upwardly through said second separation zone, combining said vstreams at the head of said second evaporation zone, withdrawing the vapors developed in said second evaporation zone, passing the remaining viscous sugar solution in a third evaporation zone maintained at a pressure of about 30 to 50 Torr., heating said third evaporation zone with the vapors withdrawn from said second evaporation zone, circulating said solution in said third evaporation zone until a sugar concentration of 60 to 75 percent has been obtained, and withdrawing said concentrated sugar solution.

5. A process for concentrating a sugar solution obtained in the hydrochloric acid sacchariiication of cellulosic materials comprising passing said solution in separate confined streams having a diameter not substantially exceeding 15 mm. through a rst evaporation zone maintained substantially at atmospheric pressure and at a temperature of about 100 to 150 C. at a rate produc- 6 ing a residence time of about .5 to 3 seconds, combiri ing said streams, drawing ot the vapors developed in said rst evaporation zone, passing the remaining solution in continuous iiow, into a second evaporation zone maintained at a pressure of about 100 to 250 Torr., heating said second evaporation zone with the vapors of said rst evaporation zone at a temperature of about to 80 C., passing the solution in separate confined streams of substantially the same diameter and at substantially the same rate as in said first evaporation zone through said second separation zone, combining said streams, withdrawing the vapors developed in said second evaporation zone, passing the remaining viscous sugar solution in a third evaporation zone maintained at a pressure of about 30 to 50 Torr., heating said third evaporation zone with the vapors withdrawn from said second evaporation zone, circulating said solution in said third evaporation zone until a sugar concentration of 60 to 75 percent has been obtained, and withdrawing said concentrated sugar solution.

6. The process deiined in claim 5 wherein said solution is passed downwardly through said rst and second evaporation zone.

References Cited in the tile of this patent UNITED STATES PATENTS 1,028,738 Kestner June 4, 1912 1,847,589 Brobeck Mar. l, 1932 FOREIGN PATENTS 480,610 Great Britain Feb. 24, 1938 

1. A PROCESS FOR CONCENTRATING A SUGAR SOLUTION OBTAINED IN THE HYDROCHLORIC ACID SCAAHARIFICATION OF CELLULOSIC MATERIALS COMPRISING PASSING SAID SOLUTION SUBSTANTIALLY UNDER ATMOSPHERIC PRESSURE UPWARDLY AT A RATE OF ABOUT 10 TO 40 M./SEC. THROUGH A FIRST SET OF NARROW VERTICAL TUBES HAVING A DIAMETER OF ABOUT 8 TO 20 MM. AND HEATED AT A TEMPERATURE OF ABOUT 100 TO 150*C., SAID RATE OF FLOW PREVENTING BACKFLOW OF SAID SOLUTION INTO SAID TUBES SEPARATING THE GENERATED VAPORS FROM THE SOLUTION, TRANSFERRING THE THUS SEPARATED SOLUTION AT SUBSTANTIALLY THE RATE OF SEPARATION, SO AS TO PREVENT ACCUMULATION THEREOF IN THE SEPARATION ZONE, CONTINUOUSLY SUBSTANTIALLY WITHOUT INTERMEDIATE STOPPAGE INTO A SECOND SET OF NARROW VERTICAL TUBES, HEATING SAID SECOND SET OF TUBES WITH SAID GENERATED VAPORS, PASSING SAID SOLUTION AT A PRESSURE OF ABOUT 100 TO 250 TORR. UPWARDLY THROUGH SAID SECOND SET OF TUBES, WITHDRAWING VAPORS FROM THE SOLUTION LEAVING SAID SECOND SET OF TUBES, FEEDING THE REMAINING SOLUTION INTO A CIRCULATING EVAPORATOR MAINTAINED AT A PRESSURE OF ABOUT 30 TO 50 TORR., HEATING SAID CIRCULATING EVAPORATOR WITH SAID WITHDRAWING VAPORS, AND DRAWING OFF COMCENTRATED SUGAR SYRUP AND HYDROCHLORIC ACID VAPORS FROM SAID CIRCULATING EVAPORATOR. 